US8304476B2 - Flame retardant resin composition and molded article thereof - Google Patents

Flame retardant resin composition and molded article thereof Download PDF

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US8304476B2
US8304476B2 US13/321,914 US201013321914A US8304476B2 US 8304476 B2 US8304476 B2 US 8304476B2 US 201013321914 A US201013321914 A US 201013321914A US 8304476 B2 US8304476 B2 US 8304476B2
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component
resin composition
flame retardant
parts
retardant resin
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US20120077910A1 (en
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Katsuhiro Yamanaka
Fumitaka Kondo
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Teijin Ltd
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Teijin Chemicals Ltd
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Priority claimed from JP2009147547A external-priority patent/JP5563249B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
    • C08K5/5333—Esters of phosphonic acids
    • C08K5/5357—Esters of phosphonic acids cyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified

Definitions

  • the present invention relates to a resin composition having flame retardancy and excellent physical properties and a molded article thereof. More specifically, it relates to a substantially halogen-free flame retardant resin composition comprising a specific organic phosphorus compound and a molded article thereof.
  • Resins such as polypropylenes (PP), acrylonitrile-butadiene-styrene (ABS), polyamides (PA6, PA66), polyesters (PET, PBT) and aromatic polycarbonates (PC) are used as raw materials for obtaining resin molded articles. These resins are produced from raw materials obtained from oil resources. In recent years, problems such as the depletion of oil resources and global environment have been concerned, and the production of a resin from a raw material obtained from biogenic matter such as a plant has been desired.
  • a resin obtained from a plant-derived raw material is regarded as a resin having a low load on the global environment from the concept “carbon neutral” which means that it is neutral in terms of the balance of carbon in view of the amount of carbon dioxide absorbed during the growth of a plant even when it is burnt after use.
  • Patent Documents 1 to 6 Various attempts have been made for the flame retardation of resins obtained from plant-derived raw materials, especially polylactic acid resin, and a certain measure of flame retardation has been attained (Patent Documents 1 to 6). However, a large amount of a flame retardant is used to flame retard these resins, whereby the physical properties of the resins are impaired.
  • a flame retardant resin composition comprising:
  • the flame retardant resin composition of the present invention will be described in more detail hereinunder.
  • the resin component (component A) contains polylactic acid.
  • the resin component (component A) contains the polylactic acid in an amount of preferably at least 50 wt %, more preferably at least 55 wt %, much more preferably at least 60 wt %.
  • the content of the polylactic acid (component A-1) in the resin component (component A) is preferably 50 to 89 wt %, more preferably 55 to 85 wt %, much more preferably 60 to 80 wt %.
  • the resin component (component A) may contain an aromatic polycarbonate resin (component A-2) and a styrene-based resin (component A-3) in addition to the polylactic acid (component A-1).
  • the content of the aromatic polycarbonate resin (component A-2) in the resin component (component A) is preferably 10 to 40 wt %, more preferably 14 to 38 wt %, much more preferably 19 to 35 wt %.
  • the content of the styrene-based resin (component A-3) in the resin component (component A) is preferably 1 to 10 wt %, more preferably 1 to 7 wt %, much more preferably 1 to 5 wt %.
  • the resin component (component A) contains 50 to 89 wt % of the polylactic acid (component A-1), 10 to 40 wt % of the aromatic polycarbonate resin (component A-2) and 1 to 10 wt % of the styrene-based resin (component A-3).
  • the polylactic acid (component A-1) includes a polymer composed of only a lactic acid unit and a lactic acid copolymer composed of a lactic acid unit and another unit.
  • the polylactic acid (component A-1) is a polymer obtained from L-lactic acid, D-lactic acid, DL-lactic acid or a mixture thereof, or L-lactide which is a cyclic dimer of L-lactic acid, D-lactide which is a cyclic dimer of D-lactic acid, meso-lactide which is a cyclic dimer of L-lactic acid and D-lactic acid or a mixture thereof.
  • the polylactic acid (component A-1) is not particularly limited, it is produced by a commonly known melt polymerization process or a combination of the melt polymerization process and a solid-phase polymerization process. Examples of the processes are disclosed by U.S. Pat. No. 1,995,970, U.S. Pat. No. 2,362,511 and U.S. Pat. No. 2,683,136, and the polylactic acid is synthesized from a cyclic dimer of lactic acid which is generally called “lactide” by ring-opening polymerization.
  • U.S. Pat. No. 2,758,987 discloses a ring-opening polymerization process in which a cyclic dimer of lactic acid (lactide) is melt polymerized.
  • the copolymer is obtained mainly from a lactic acid.
  • examples of the copolymer include a lactic acid-hydroxycarboxylic acid copolymer and a lactic acid-aliphatic polyhydric alcohol-aliphatic polybasic acid copolymer.
  • hydroxycarboxylic acid examples include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid and 6-hydroxycaproic acid. They may be used alone or in combination of two or more.
  • a cyclic ester intermediate of hydroxycarboxylic acid such as glycolide which is a dimer of glycolic acid or s-caprolactone which is a cyclic ester of 6-hydroxycaproic acid may also be used.
  • aliphatic polyhydric alcohol examples include aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, neopentyl glycol, decamethylene glycol and 1,4-cyclohexane dimethanol. They may be used alone or in combination of two or more.
  • aliphatic polybasic acid examples include aliphatic dibasic acids such as succinic acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid. They may be used alone or in combination of two or more.
  • the hydroxycarboxylic acid copolymer is generally synthesized by the ring-opening polymerization of lactide or a cyclic ester intermediate of a hydroxycarboxylic acid, and its production process is disclosed by U.S. Pat. No. 3,635,956 and U.S. Pat. No. 3,797,499.
  • U.S. Pat. No. 5,310,865 discloses a process in which lactic acid or a mixture of lactic acid and hydroxycarboxylic acid is used as a raw material and directly dehydrated and polycondensed.
  • 4,057,537 discloses a ring-opening polymerization process in which cyclic dimers of lactic acid and an aliphatic hydroxycarboxylic acid, for example, lactide and glycolide, and ⁇ -caprolactone are melt polymerized in the presence of a catalyst.
  • a lactic acid-based resin is produced directly by dehydration polycondensation and not ring-opening polymerization
  • a polylactic acid copolymer is obtained by carrying out the azeotropic dehydration condensation of a lactic acid and optionally another hydroxycarboxylic acid preferably in the presence of an organic solvent, especially a phenyl ether-based solvent.
  • Polymerization is preferably carried out by removing water from the solvent distilled out by azeotropy to return a substantially anhydrous solvent into a reaction system.
  • U.S. Pat. No. 5,428,126 discloses a process in which a mixture of lactic acid, an aliphatic dihydric alcohol and an aliphatic dibasic acid is directly dehydrated and condensed.
  • European Patent No. 0712880A2 discloses a process in which a polymer of polylactic acid and a polymer of an aliphatic dihydric alcohol and an aliphatic dibasic acid are condensed in the presence of an organic solvent.
  • a suitable molecular weight control agent, a branching agent and a modifier may be added for the production of the lactic acid copolymer.
  • L-lactic acid which is composed of only a lactic acid unit is preferably used in the present invention, and poly-L-lactic acid which is obtained mainly from L-lactic acid is particularly preferred.
  • L-lactic acid contains D-lactic acid which is an optical isomer, and its content is preferably not more than 15 wt %, more preferably not more than 10 wt %, particularly preferably not more than 5 wt %.
  • the optical isomer is advantageously used for a molded article which is desired to be soft, it is not preferred for a composition which requires heat resistance.
  • aromatic polycarbonate resin examples include polycarbonate resins obtained by an interfacial polymerization reaction between a dihydroxyaryl compound and phosgene in the presence of a solvent such as methylene chloride and polycarbonate resins obtained by a transesterification reaction between a dihydroxyaryl compound and diphenyl carbonate.
  • a typical example of the aromatic polycarbonate resin is obtained from a reaction between 2,2′-bis(4-hydroxyphenyl)propane and phosgene.
  • dihydroxyaryl compound which is a raw material of the aromatic polycarbonate resin examples include bis(4-hydroxyphenyl)methane, 1,1′-bis(4-hydroxyphenyl)ethane, 2,2′-bis(4-hydroxyphenyl)propane, 2,2′-bis(4-hydroxyphenyl)butane, 2,2′-bis(4-hydroxyphenyl)octane, 2,2′-bis(4-hydroxy-3-methylphenyl)propane, 2,2′-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2′-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2′-bis(4-hydroxy-3-cyclohexylphenyl)propane, 2,2′-bis(4-hydroxy-3-methoxyphenyl)propane, 1,1′-bis(4-hydroxyphenyl)cyclopentane, 1,1′-bis(4-hydroxyphenyl)cyclopentane
  • the dihydroxyaryl compound is preferably selected from bisphenols which form an aromatic polycarbonate having high heat resistance, bis(hydroxyphenyl)alkanes such as 2,2′-bis(4-hydroxyphenyl)propane, bis(hydroxyphenyl)cycloalkanes such as bis(4-hydroxyphenyl)cyclohexane, dihydroxydiphenyl sulfide, dihydroxydiphenyl sulfone and dihydroxydiphenyl ketone.
  • the dihydroxyaryl compound is particularly preferably 2,2′-bis(4-hydroxyphenyl)propane which forms a bisphenol A type aromatic polycarbonate.
  • part of bisphenol A may be substituted by another dihydroxyaryl compound.
  • a reaction is generally carried out in the presence of an acid binder and an organic solvent.
  • the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and amine compounds such as pyridine.
  • the organic solvent include halogenated hydrocarbons such as methylene chloride and chlorobenzene.
  • a catalyst such as tertiary amine or quaternary amine may be used to promote the reaction.
  • a terminal capping agent such as phenol or alkyl-substituted phenol as exemplified by p-tert-butylphenol is desirably used as a molecular weight control agent.
  • the reaction temperature is generally 0 to 40° C.
  • the reaction time is several minutes to 5 hours
  • pH during the reaction is preferably kept at 10 or more. All the terminals of the obtained molecular chain do not need to have a structure derived from the terminal capping agent.
  • transesterification reaction in which a diester carbonate is used as the carbonate precursor, a predetermined amount of a dihydric phenol is stirred together with the diester carbonate in the presence of an inert gas under heating, and the formed alcohol or phenol is distilled off.
  • the reaction temperature which differs according to the boiling point of the formed alcohol or phenol is generally 120 to 350° C.
  • the reaction is completed while the formed alcohol or phenol is distilled off by reducing the pressure from the initial stage.
  • a terminal capping agent is added at the same time as the dihydric phenol in the initial stage of the reaction or in the middle of the reaction.
  • An existing known catalyst which is used for a transesterification reaction may be used to promote the reaction.
  • diester carbonate used in this transesterification reaction examples include diphenyl carbonate, dinaphthyl carbonate, dimethyl carbonate, diethyl carbonate and dibutyl carbonate. Out of these, diphenyl carbonate is particularly preferred.
  • the molecular weight of the aromatic polycarbonate resin does not need to be particularly limited but if it is too low, strength becomes unsatisfactory and if it is too high, melt viscosity becomes high, thereby making molding difficult.
  • the molecular weight of the aromatic polycarbonate resin is generally 1.0 ⁇ 10 4 to 5.0 ⁇ 10 4 , preferably 1.5 ⁇ 10 4 to 3.0 ⁇ 10 4 in terms of viscosity average molecular weight.
  • the viscosity average molecular weight (M) is obtained by inserting the specific viscosity ( ⁇ sp ) of a solution prepared by dissolving 0.7 g of the polycarbonate resin in 100 ml of methylene chloride at 20° C. into the following equation.
  • the styrene-based resin (component A-3) is a homopolymer or copolymer of an aromatic vinyl monomer such as styrene, ⁇ -methylstyrene or vinyl toluene. It may be a copolymer of one of these monomers and a vinyl monomer such as acrylonitrile or methyl methacrylate. It may also be a graft polymer obtained by graft polymerizing a diene-based rubber such as polybutadiene, ethylene.propylene-based rubber or acrylic rubber with styrene and/or a styrene derivative, or styrene and/or a styrene derivative with another vinyl monomer.
  • a diene-based rubber such as polybutadiene, ethylene.propylene-based rubber or acrylic rubber with styrene and/or a styrene derivative, or styrene and/or a sty
  • styrene-based resin examples include polystyrene, impact-resistant polystyrene (HIPS), acrylonitrile.styrene copolymer (AS resin), acrylonitrile. butadiene.styrene copolymer (ABS resin), methyl methacrylate.butadiene.styrene copolymer (MBS resin), methyl methacrylate.acrylonitrile.butadiene.styrene copolymer (MABS resin), acrylonitrile.acrylic rubber. styrene copolymer (AAS resin), acrylonitrile.ethylene propylene-based rubber.styrene copolymer (AES resin), and mixtures thereof. It is preferably an acrylonitrile.styrene copolymer (AS resin), its production process is not particularly limited, and it is obtained by known bulk polymerization, bulk suspension polymerization, solution polymerization or emulsion polymerization.
  • the organic phosphorus compound (component B) is represented by the following formula (1).
  • the phenyl group may have a substituent.
  • the phenyl group has no substituent.
  • the phenyl group in the formula (1) may have a substituent at any part other than the part bonded to a methylene group through a carbon atom on the aromatic ring.
  • the substituent include methyl group, ethyl group, propyl group (including an isomer thereof), butyl group (including an isomer thereof) and aryl group having 6 to 14 carbon atoms and bonded to the aromatic ring through oxygen, sulfur or aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • the organic phosphorus compound (component B) represented by the above formula (1) has an extremely excellent flame retarding effect for the polylactic acid. As far as the inventors of the present invention know, the halogen-free flame retardation of the polylactic acid has been difficult with a small amount of a flame retardant and has had a large number of problems to be solved for practical use.
  • the flame retardation of the polylactic acid is easily attained by using a small amount of the above organic phosphorus compound (component B) alone without impairing the characteristic properties of the polylactic acid.
  • component B organic phosphorus compound
  • a fluorine-containing resin or other additives may be used in addition to the component B in order to reduce the amount of the component B and improve the flame retardancy, physical properties and chemical properties of a molded article and for other purposes.
  • component B A description is subsequently given of the method of synthesizing the above organic phosphorus compound (component B).
  • component B may be produced by a method except for the method described below.
  • the component B is obtained by reacting phosphorus trichloride with pentaerythritol, treating the oxidized reaction product with an alkali metal compound such as sodium methoxide, and reacting an aralkyl halide with the reaction product.
  • the component B may also be obtained by a method in which pentaerythritol is reacted with aralkyl phosphonic acid dichloride, or a method in which pentaerythritol is reacted with phosphorus trichloride and then the obtained compound is reacted with an aralkyl alcohol to carry out Arbuzov rearrangement at a high temperature.
  • the latter reaction is disclosed in U.S. Pat. No. 3,141,032, JP-A 54-157156 and JP-A 53-39698.
  • the organic phosphorus compound (component B) may be synthesized not only by these methods but also by modified methods thereof and other methods. More specific synthesizing methods will be described in Preparation Examples which are given hereinafter.
  • An organic phosphorus compound (component B) which has an acid value of not more than 0.7 mgKOH/g, preferably not more than 0.5 mgKOH/g is used.
  • the acid value of the component B is most preferably not more than 0.4 mgKOH/g.
  • the term “acid value” means the amount (mg) of KOH required for neutralizing the acid component contained in 1 g of a sample (component B).
  • the component B having an HPLC purity of preferably at least 90%, more preferably at least 95% is used.
  • the component B having such a high HPLC purity is excellent in the flame retardancy, color and thermal stability of a molded article obtained therefrom.
  • the HPLC purity of the component B can be effectively measured by the following method.
  • the Develosil ODS-7 having a length of 300 mm and a diameter of 4 mm of Nomura Chemical Co., Ltd. was used as a column, and the column temperature was set to 40° C.
  • a mixed solution of acetonitrile and water in a volume ratio of 6:4 was used as a solvent, and 5 ⁇ l of the solution was injected.
  • An UV-260 nm detector was used.
  • the method of removing impurities contained in the component B is not particularly limited but a method in which repulp cleaning (cleaning with a solvent and filtration are repeated several times) is carried out with a solvent such as water or methanol is the most effective and economically advantageous.
  • the content of the organic phosphorus compound (component B) is 10 to 50 parts by weight, preferably 10 to 40 parts by weight, more preferably 15 to 35 parts based on 100 parts by weight of the resin component (component A).
  • the preferred range of the content of the component B is determined according to the desired level of flame retardancy and the type of the resin component (component A).
  • Other components except for the components A and B constituting the composition may be optionally used as long as the object of the present invention is not impaired.
  • the content of the component B can be changed by using another flame retardant, a retarding aid or a fluorine-containing resin. In most cases, the content of the component B can be reduced by using these substances.
  • the hydrogenated styrene-based thermoplastic elastomer (component C) is a terpolymer obtained by hydrogenating a polymer containing a conjugated diene in the recurring unit.
  • the method of polymerizing a polymer containing a conjugated diene to be hydrogenated in the recurring unit is not particularly limited, and the hydrogenated styrene-based thermoplastic elastomer may be produced by prior art such as anion polymerization, cation polymerization, free radical polymerization, ligand polymerization, solution polymerization or emulsion polymerization.
  • Examples of the polymer containing a conjugated diene in the recurring unit include a styrene-butadiene copolymer, styrene-isoprene copolymer and styrene-isopentadiene copolymer.
  • the styrene-butadiene copolymer is preferred.
  • the hydrogenation method of the hydrogenated styrene-based thermoplastic elastomer (component C) is not particularly limited and can be carried out based on prior art disclosed, for example, by JP-A 2007-301449.
  • Examples of the hydrogenated styrene-based thermoplastic elastomer (component C) include a styrene-ethylene-butylene-styrene terpolymer (SEBS) obtained by hydrogenating a styrene-butadiene copolymer, styrene-ethylene-propylene-styrene terpolymer (SEPS) obtained by hydrogenating a styrene-isoprene copolymer, and styrene-ethylene-propylene-styrene terpolymer (SEEPS) obtained by hydrogenating a styrene-isopentadiene copolymer.
  • SEEPS styrene-ethylene-butylene-styrene terpolymer
  • SEES styrene-ethylene-butylene-styrene terpolymer obtained by hydrogenating a styrene-butadiene copolymer
  • the content of the hydrogenated styrene-based thermoplastic elastomer (component C) is 5 to 30 parts by weight, preferably 10 to 20 parts by weight based on 100 parts by weight of the component A.
  • Talc (component D) is not particularly limited, and commercially available talc may be generally used.
  • the talc is preferably talc having a particle diameter of 500 to 1,000 mesh, particularly preferably talc having a particle diameter of 600 to 900 mesh.
  • the content of the talc (component D) is 1 to 10 parts by weight, preferably 2 to 8 parts by weight based on 100 parts by weight of the resin component (component A).
  • the flame retardant resin composition of the present invention can be prepared by pre-mixing together the resin component (component A), the organic phosphorus compound (component B), the hydrogenated styrene-based thermoplastic elastomer (component C) and talc (component D) and optionally other components and melt mixing them together.
  • Premixing may be carried out by using a twin-cylinder mixer, super mixer, super floater or Henschel mixer.
  • Melt mixing may be carried out by using a kneader.
  • a melt mixer such as a kneader, or single-screw or double-screw extruder.
  • a method in which a double-screw extruder is used to melt the resin composition at 190 to 250° C., preferably 200 to 240° C. and a liquid component is injected into the resin composition by a side feeder, extruded and pelletized by a pelletizer is particularly preferably employed.
  • the flame retardant resin composition of the present invention contains substantially no halogen, has extremely high flame retardancy and is useful as a material for forming various molded articles such as home electric appliance parts, electric and electronic parts, auto parts, mechanical and electromechanical parts, and cosmetic containers. More specifically, it can be advantageously used in breaker parts, switch parts, motor parts, ignition coil cases, power plugs, power receptacles, coil bobbins, connectors, relay cases, fuse cases, flyback transformer parts, focus block parts, distributor caps and harness connectors.
  • housings, casings and chassis which are becoming thinner, for example, housings for electric and electronic products (for example, home electric appliances and OA equipment such as telephones, personal computers, printers, facsimiles, copiers, TV, video decks and audio equipment, and parts thereof), casings and chassis. It is particularly useful for mechanical and electromechanical parts for home electric appliances and OA equipment, such as printer housings, fixing unit parts and facsimiles all of which require excellent heat resistance and flame retardancy.
  • the molding technique is not particularly limited and may be injection molding, blow molding or press molding. However, preferably, a pellet resin composition is injection molded by using an injection molding machine.
  • the flame retardant resin composition of the present invention can achieve at least V-2 rating in UL-94 flame retardancy level.
  • the present invention includes a method of improving the flame retardancy of a resin composition, comprising adding a compound represented by the formula (1) to a resin composition containing polylactic acid.
  • test piece having a thickness of 1/16 inch (1.6 mm) was used to evaluate its flame retardancy in accordance with a vertical burn test specified in US UL-94 standards as a measure of evaluating flame retardancy.
  • the UL-94 vertical burn test is made on a set of five test pieces, and a flame is applied to each of the specimens for 10 seconds twice. This is not applied to a test piece which is burnt down with the first flame application. After a first time of flaming combustion, the combustion time after the flame is removed is measured, and a second flame is applied after extinction. After the second flame application, the combustion time after the flame is removed is measured. A total of 10 combustion times can be measured by tests on a set of five specimens. When burning stops within 10 seconds, the total of 10 combustion times is 50 seconds or less, and cotton is not ignited by flaming drips from any specimen, the specimen is rated V-0.
  • a sample was dissolved in a mixed solution of acetonitrile and water in a volume ratio of 6:4, and 5 ⁇ l of the resulting solution was injected into a column.
  • the Develosil ODS-7 having a length of 300 mm and a diameter of 4 mm of Nomura Chemical Co., Ltd. was used as the column, and the column temperature was set to 40° C.
  • a UV-260 nm detector was used.
  • the nuclear magnetic resonance of a phosphorus atom was measured (DMSO-d 6 , 162 MHz, integrated number of times of 3072) with a nuclear magnetic resonance measuring instrument (JNM-AL400 of JEOL Ltd.) to obtain an integral area ratio as the 31 PNMR purity of the phosphorus compound.
  • the precipitated crystal was separated by filtration and washed with 20 mL of xylene twice.
  • the obtained roughly purified product and 40 mL of methanol were fed to a reactor having a condenser and a stirrer and refluxed for about 2 hours.
  • the crystal was cooled to room temperature, separated by filtration and washed with 20 mL of methanol, and the obtained filtrate was dried at 120° C. and 1.33 ⁇ 10 2 Pa for 19 hours to obtain a white flaky crystal.
  • polylactic acid resin 4032D of Nature Works Co., Ltd.; poly-L-lactic acid resin
  • PLA polylactic acid resin
  • PC polycarbonate resin
  • SAN styrene acrylonitrile copolymer
  • SEBS SEBS copolymer
  • talc particle diameter of 800 mesh
  • PLA as the component A-1 was dried at 50° C. under reduced pressure for 24 hours or more and other components were dried at 70° C. under reduced pressure for 24 hours or more.
  • PLA as the component A-1 was dried at 50° C. under reduced pressure for 24 hours or more and other components were dried at 70° C. under reduced pressure for 24 hours or more.
  • the obtained pellet was dried at 80° C. with a hot air drier for 3 hours and molded by an injection molding machine (clamping force of 100 t).
  • the flame retardant resin composition of the present invention and a molded article formed therefrom have the following advantages as compared with a conventional polylactic acid composition.
  • the flame retardant resin composition of the present invention is useful as a material for forming various molded articles such as home electric appliance parts, electric and electronic parts, auto parts, mechanical and electromechanical parts, and cosmetic containers.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
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JP2009126391A JP5378881B2 (ja) 2009-05-26 2009-05-26 難燃性樹脂組成物およびそれからの成形品
JP2009-147547 2009-06-22
JP2009147547A JP5563249B2 (ja) 2009-06-22 2009-06-22 難燃性樹脂組成物およびそれからの成形品
PCT/JP2010/058941 WO2010137632A1 (fr) 2009-05-26 2010-05-20 Composition de résine ignifuge et article moulé a partir de celle-ci

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Cited By (3)

* Cited by examiner, † Cited by third party
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US20130281585A1 (en) * 2010-10-27 2013-10-24 Katsuhiro Yamanaka Flame retardant resin composition and molded article thereof
US9309403B2 (en) 2012-10-17 2016-04-12 Polyone Corporation Heat resistant, flame retardant polylactic acid compounds
US9534116B2 (en) 2012-10-17 2017-01-03 Polyone Corporation Flame retardant polylactic acid compounds

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JP6060681B2 (ja) * 2012-09-11 2017-01-18 富士ゼロックス株式会社 樹脂組成物、および樹脂成形体
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JP2023025808A (ja) * 2021-08-11 2023-02-24 ミュン ゴン キム 射出成形靴底材料、それを含む靴底及びその製造方法並びに用途

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5060481A (fr) 1973-09-25 1975-05-24
US3962377A (en) 1973-09-25 1976-06-08 Ciba-Geigy Corporation 2,3,5-Trialkyl-4-hydroxybenzylphosphonates and phosphinates
JPS5212329A (en) 1975-07-15 1977-01-29 Ciba Geigy Ag Fireeretardant polyester synthetic fiber and its manufacture
US4069200A (en) 1974-07-26 1978-01-17 Ciba-Geigy Corporation 2,3,5-Trialkyl-4-hydroxybenzylphosphonates and phosphinates
US4093588A (en) 1974-10-07 1978-06-06 Ciba-Geigy Corporation Hindered phenolic cyclic phosphonates and stabilized compositions
JP2001164014A (ja) 1999-12-07 2001-06-19 Ado Cosmic Kk 生分解性難燃断熱材
JP2003160722A (ja) 2001-09-17 2003-06-06 Teijin Chem Ltd 難燃性樹脂成形物およびそれからの成形品
JP2004131580A (ja) 2002-10-10 2004-04-30 Teijin Chem Ltd 難燃性樹脂組成物およびそれからの成形品
US20040127611A1 (en) 2001-05-15 2004-07-01 Katsuhiro Yamanaka Flame-retardant resin composition and molded article therefrom
JP2004210968A (ja) 2003-01-06 2004-07-29 Teijin Chem Ltd 難燃性樹脂組成物およびそれからの成形品
JP2004277552A (ja) 2003-03-14 2004-10-07 Toray Ind Inc 難燃性生分解性樹脂架橋発泡体
WO2004087809A1 (fr) 2003-03-28 2004-10-14 Ps Japan Corporation Composition de resine styrene ignifuge
JP2005023260A (ja) 2003-07-04 2005-01-27 Toray Ind Inc 電気・電子部品
JP2005139441A (ja) 2003-10-15 2005-06-02 Mitsubishi Plastics Ind Ltd 射出成形体
US20070142503A1 (en) 2003-10-14 2007-06-21 Sony Corporation Flame-retardant injection-molded
JP2007191546A (ja) 2006-01-18 2007-08-02 Teijin Chem Ltd 自動車部品
JP2007246730A (ja) 2006-03-16 2007-09-27 Du Pont Mitsui Polychem Co Ltd 難燃性樹脂組成物
JP2008019294A (ja) 2006-07-11 2008-01-31 Unitika Ltd 難燃性ポリ乳酸樹脂組成物
JP5060481B2 (ja) 2005-08-05 2012-10-31 エスビー エレクトロニクス，インコーポレイテッド 熱誘発性損傷に対して耐性のあるキャパシタ及び方法

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1995970A (en) 1931-04-04 1935-03-26 Du Pont Polymeric lactide resin
US2362511A (en) 1939-11-21 1944-11-14 Du Pont Modified glycolide resins
US2683136A (en) 1950-10-25 1954-07-06 Du Pont Copolymers of hydroxyacetic acid with other alcohol acids
US2758987A (en) 1952-06-05 1956-08-14 Du Pont Optically active homopolymers containing but one antipodal species of an alpha-monohydroxy monocarboxylic acid
US3141032A (en) 1963-01-23 1964-07-14 Union Carbide Corp Dialkyl pentaerythritol diphosphonates and phosphite phosphonates
US3635956A (en) 1968-03-01 1972-01-18 Squibb & Sons Inc Benzothiazines related compounds derivatives and salts thereof
US3797499A (en) 1970-05-13 1974-03-19 Ethicon Inc Polylactide fabric graphs for surgical implantation
US4057537A (en) 1975-01-28 1977-11-08 Gulf Oil Corporation Copolymers of L-(-)-lactide and epsilon caprolactone
US4154721A (en) 1976-09-21 1979-05-15 Borg-Warner Corporation Flame-retardant phosphonate compositions
US4178281A (en) 1978-05-30 1979-12-11 Borg-Warner Corporation Flame-retardant polycarbonate compositions
DE69230032T2 (de) 1991-12-19 2000-02-03 Mitsui Chemicals Inc Polyhydroxycarbonsäure und verfahren zu ihrer herstellung
US5401796A (en) 1993-04-02 1995-03-28 Mitsui Toatsu Chemicals, Inc. Aliphatic polyester and preparation process thereof
US5637631A (en) 1994-11-17 1997-06-10 Mitsui Toatsu Chemicals, Inc. Preparation process of degradable polymer
JP4536993B2 (ja) * 2002-06-19 2010-09-01 帝人化成株式会社 難燃性樹脂組成物およびそれからの成形品
CN101023133B (zh) * 2004-09-17 2011-11-02 东丽株式会社 树脂组合物和由其形成的成型品
JP4921849B2 (ja) 2006-05-09 2012-04-25 台橡股▲ふん▼有限公司 共役ジエン重合体の水素化方法
JP5371974B2 (ja) * 2008-05-27 2013-12-18 帝人株式会社 難燃性樹脂組成物およびそれからの成形品

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5060481A (fr) 1973-09-25 1975-05-24
US3962377A (en) 1973-09-25 1976-06-08 Ciba-Geigy Corporation 2,3,5-Trialkyl-4-hydroxybenzylphosphonates and phosphinates
GB1476994A (en) 1973-09-25 1977-06-16 Ciba Geigy Ag 2,3,5-tri-substituted-4-hydroxybenzyl-phosphonates and phos phinates
US4069200A (en) 1974-07-26 1978-01-17 Ciba-Geigy Corporation 2,3,5-Trialkyl-4-hydroxybenzylphosphonates and phosphinates
US4093588A (en) 1974-10-07 1978-06-06 Ciba-Geigy Corporation Hindered phenolic cyclic phosphonates and stabilized compositions
JPS5212329A (en) 1975-07-15 1977-01-29 Ciba Geigy Ag Fireeretardant polyester synthetic fiber and its manufacture
GB1515223A (en) 1975-07-15 1978-06-21 Ciba Geigy Ag Flame-proofing of polyester fibres
JP2001164014A (ja) 1999-12-07 2001-06-19 Ado Cosmic Kk 生分解性難燃断熱材
US20040127611A1 (en) 2001-05-15 2004-07-01 Katsuhiro Yamanaka Flame-retardant resin composition and molded article therefrom
JP2003160722A (ja) 2001-09-17 2003-06-06 Teijin Chem Ltd 難燃性樹脂成形物およびそれからの成形品
JP2004131580A (ja) 2002-10-10 2004-04-30 Teijin Chem Ltd 難燃性樹脂組成物およびそれからの成形品
JP2004210968A (ja) 2003-01-06 2004-07-29 Teijin Chem Ltd 難燃性樹脂組成物およびそれからの成形品
JP2004277552A (ja) 2003-03-14 2004-10-07 Toray Ind Inc 難燃性生分解性樹脂架橋発泡体
WO2004087809A1 (fr) 2003-03-28 2004-10-14 Ps Japan Corporation Composition de resine styrene ignifuge
US20060258816A1 (en) 2003-03-28 2006-11-16 Shigeru Endo Flame-retardant styrenic resin composition
JP2005023260A (ja) 2003-07-04 2005-01-27 Toray Ind Inc 電気・電子部品
US20070142503A1 (en) 2003-10-14 2007-06-21 Sony Corporation Flame-retardant injection-molded
JP2005139441A (ja) 2003-10-15 2005-06-02 Mitsubishi Plastics Ind Ltd 射出成形体
JP5060481B2 (ja) 2005-08-05 2012-10-31 エスビー エレクトロニクス，インコーポレイテッド 熱誘発性損傷に対して耐性のあるキャパシタ及び方法
JP2007191546A (ja) 2006-01-18 2007-08-02 Teijin Chem Ltd 自動車部品
JP2007246730A (ja) 2006-03-16 2007-09-27 Du Pont Mitsui Polychem Co Ltd 難燃性樹脂組成物
JP2008019294A (ja) 2006-07-11 2008-01-31 Unitika Ltd 難燃性ポリ乳酸樹脂組成物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
English translation of the International Preliminary Report on Patentability and Written Opinion dated Dec. 12, 2011.
International Search Report issued Sep. 7, 2010 in International (PCT) Application No. PCT/JP2010/058941.

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130281585A1 (en) * 2010-10-27 2013-10-24 Katsuhiro Yamanaka Flame retardant resin composition and molded article thereof
US9309403B2 (en) 2012-10-17 2016-04-12 Polyone Corporation Heat resistant, flame retardant polylactic acid compounds
US9534116B2 (en) 2012-10-17 2017-01-03 Polyone Corporation Flame retardant polylactic acid compounds

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CN102449065A (zh) 2012-05-09
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EP2436730A4 (fr) 2015-04-22
TW201105740A (en) 2011-02-16
EP2436730A1 (fr) 2012-04-04
US20120077910A1 (en) 2012-03-29
WO2010137632A1 (fr) 2010-12-02

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